Structural transition of pentacene monolayer on Ga bilayer: From brick-wall structure to herringbone pattern of molecular dimers

Utilizing the substrate of Ga bilayer grown on Si(1 1 1)-√3 × √3-Ga, we have investigated the structural transition of pentacene monolayer induced by moderate annealing. Short-range ordering has been observed in the monolayer pentacene deposited at room temperature. Annealing the sample at ∼350 K produced ordered pentacene monolayer with the “brick-wall” adsorption pattern. The STM images with sub-molecular resolution revealed that the orbital symmetry of the HOMO is reduced from D_2h to C_2v, due to the substrate-molecule interaction, while the deeper HOMO-1 orbital remains intact. Further annealing at ∼400 K led to the formation of molecular dimers as well as the structural transition from “brick-wall” packing to “herringbone” pattern.